DE69915892T2 - SPANDEXFIBER POLYURETHANE UREA POLYMERE MANUFACTURED BY USING 1,3-DIAMINOPENTAN AS CHAIN EXTENDER - Google Patents

Description

The The present invention relates to novel polyurethane ureas and spandex made from it, and more specifically polyurethane ureas, which were chain extended with 1,3-diamine pentane.

1,3-diaminopentane has recently become commercially available. An older one Revelation over its use in the manufacture of spandex is not known. JP-A-03-279415 (1991) discloses the use of asymmetric Diamines in amounts up to 30 mol.% In mixtures with symmetrical Diamines, for a good stability to grant the solution viscosity. The U.S. Patent 5,472,634 to Hart discloses the use of 1,3-diamino pentane in an amount of 15% to 30 mol.% of the total chain extender for Production of polyurethaneurea dispersions for coating compositions Water-based.

The composition of the present invention is a polyurethaneurea polymer based on:
a polymeric glycol selected from polyether glycols and polyester glycols, wherein the polyether glycol is selected from the group consisting of a homopolymer of tetrahydrofuran (THF) and a copolymer of tetrahydrofuran and 3-methyltetrahydrofuran (3-MeTHF);
1,1'-methylenebis (4-isocyanatobenzene); such as
one or more diamine chain extender (s) wherein one of the diamines is 1,3-diaminopentane (1,3-DAP) present in an amount of at least 5 mole percent of the mixture of the diamines, and wherein the other diamine is ethylene diamine is.

In the case, that the polymeric glycol is a polyether glycol depends Range of terminating conditions from the amount of 1,3-DAP present in the mixture of diamine and depends on the type of glycol and is determined as follows:

In in the case where the polymeric glycol is a polyester glycol the range of relationships of the diisocyanate to the glycol at 1.5 to 3.7.

Textile sheet or yarns containing spandex and non-elastomeric fibers typically with heat or steam to "fix" the fabric or yarn. This mediates the textile fabric or the yarn, good dimensional stability and fassoniert the finished garment. One good efficiency of steam and heat fixation allows shorter fixing times and / or lower fixing temperatures. As a result, it is possible operate the fixing process more economical and textile fabrics and yarns can be fixed even if they contain fibers that only tolerate lower temperatures.

"Spandex" as used herein has its usual Meaning, d. H. a synthetic fiber in which the fiber-forming substance a long chain of synthetic elastomer that is at least 85 wt .-% of a segmented polyurethane.

The Polyurethane is usually made by reacting a polymeric Glycol with a diisocyanate to produce an NCO-terminated Prepolymer or "capped Glycols, "dissolve the capped glycol in a suitable solvent, such as Dimethylacetamide ("DMAc"), dimethylformamide or N-methylpyrrolidone, and reacting the capped glycol with one or more bifunctional chain extenders. polyurethane ureas are generated when the chain extenders are diamines. The molar ratio of Diisocyanate to polymeric glycol is referred to as a "terminating ratio". To control the mass can work together with the chain extender adding a minor amount of monofunctional secondary amine, such as diethylamine. The polymer solution can then under Production of spandex be spun dry or wet.

It has been found that 1,3-diaminopentane (1,3-DAP) can be used in an amount of at least about 5 mole percent with other diamine chain extenders to improve the properties of the spandex which can be varied to suit the requirements of the user by varying the amount of 1,3-diaminopentane. It has also been surprisingly found that the use of 1,3-DAP in an amount of at least about 35 mole percent, with any remaining chain extenders being ethylene diamine, gives a spandex having superior steam and heat fixability. Due to the higher steam and heat fixability that can be obtained, amounts of at least about 60 mole percent 1,3-diaminopentane are preferred. If another chain extender is used together with 1,3-diaminopentane, this chain extender is ethylene diamine. To control the molecular weight of the polyurethane, small amounts of primary and / or secondary monoamines can be added. Such amines as chain terminators can generally be added as a mixture with the chain extender. Preferred is diethylamine. Optionally, a minor amount of crosslinking agent may be included, with the inclusion of a minor amount of a trifunctional amine, such as diethylenetriamine, in the mixture of chain extender / chain terminator.

suitable polymeric glycols for the practice of the present invention are polyester diols and polyether diols. The latter can of tetrahydrofuran, 3-methyltetrahydrofuran and copolymers thereof be derived. When using such a copolymer can the amount of 3-methyltetrahydrofuran present in the range of 4% to 20 mol% and preferably in the range of 10% to 15 mol.% Are.

to Preparation of the spandex of the present invention also usable are glycol terminated polyesters. These close the Reaction products of ethylene glycol, tetramethylene glycol, butylene diol, diethylene glycol and / or 2,2-dimethyl-1,3-propanediol and the like with diacids, such as adipic acid, succinic acid, 1,12-dodecanedioic and copolymers thereof. Polyester glycols differing from the ring opening of ε-caprolactone and δ-valerolactone can derive also apply. The polymeric reaction product of 2,2-dimethyl-1,3-propanediol with 1,12-dodecanedioic acid, which is poly (2,2-dimethylpropylendodecanoate) and the copolymeric reaction product of ethylene glycol, Butylene diol and adipic acid, which is polyethylene-co-butylene adipate) are here are preferred.

The Diisocyanate used in the present invention is 1,1'-methylenebis (4-isocyanatobenzene) (MDI).

The in the present invention used terminating conditions are in the range of 1.5 to 3.7. The terminating ratio becomes elevated, when the proportion of 1,3-diaminopentane in a mixture of chain extenders elevated becomes. If the scheduling ratio is too small, it is difficult to spin the polyurethaneurea to spandex. Unless the terminating relationship is too big is the elongation at break spandex too low. If the polymeric glycol is a homopolymer of THF and 1,3-diaminopentane in an amount of approximately 50% to 90 mole% of the total chain extender is present terminating ratio in the range of 1.6 to 2.5. If the polymeric glycol is a copolymer of tetrahydrofuran and 3-methyltetrahydrofuran and 1,3-diaminopentane in a lot of approximate 50% to 90 mole% of the total chain extender is present terminating ratio in the range of 2.2 to 3.7.

It were the following test methods applied:

Of the Total isocyanate content of the terminated glycols was determined by the method by S. Siggia, "Quantitative Organic Analysis via Functional Group, 3rd Ed., Wiley & Sons, New York, pp. 559-561 (1963) measured.

The strength and elasticity properties of the spandex were measured according to the general method of standard ASTM D 2731-72 using an Instron tensile testing machine (Instron Corp., Canton MA). For each of the measurements, three 5 cm (2 inch) gauge filaments and zero to 300% strain cycles were used. The samples were loaded 5 times at a constant strain rate of 50 cm per minute. The stress, ie the tension on the spandex during the first stretch, was measured at the first cycle at 200% elongation and recorded in 10 ^-3 Newtons per Tex. The decrease load is the tension at 200% elongation at the fifth unload cycle and is also recorded at 10 ^-3 Newton per tex. The relative elongation at break was measured at the sixth stretch cycle.

To measure the heat setting efficiency, the spandex specimens are clamped in a 10 cm frame and stretched 3.5 times (250%). The frame (with sample) is set horizontally in a preheated to 190 ° C oven for 90 seconds. The samples were allowed to relax and open the frame Cool room temperature. The still on the frame samples were dipped for 30 min in boiling water. The frame and samples were removed from the bath and allowed to dry. The length of the yarn samples was measured and the heat fixation efficiency was calculated from the following equation:

each Sample was tested 4 times and the results averaged.

To determine the vapor fixation, which is a hosiery processing simulation and hosiery shaping operation, a sample of a selected length in a straight, unstretched condition, Yo (conveniently 10 cm) was 3 times the original one Length stretched for about 2 minutes and then relaxed. This simulated a re-spinning operation that involves stretching the spandex while it is being wound with a conventional yarn. The thus stretched and relaxed spandex test sample was then placed in a bath of boiling water for 30 minutes in a relaxed state. With this exposure to boiling water, a staining operation is simulated. The sample was then removed from the bath, dried and stretched 2 times its relaxed length after the bath. Still in this stretched condition, the sample was exposed for 30 seconds to a steam atmosphere at 69 kPa (10 psig) over-pressure at 110 ° C. Steam treatment simulates the stocking operation. After removal from the steam atmosphere, the sample was allowed to dry, after which its straight, unstressed length, Yf, was measured. The steam fixation (% SS) was then calculated according to the formula: % SS = 100 (Yf - Yo) / Yo

A high percent steam fixation is a desired feature.

The viscosity the solution was made according to the general method ASTM D1343-69 with the falling ball viscometer Model DV-8 (Duratech Corp., Waynesboro, VA.) With one operation at 40 ° C certainly.

EXAMPLES

In In the examples, the co-chain extender used with 1,3-diaminopentane (or other branched chain extender as in the case of Example 3) ethylenediamine. The 1,3-diaminopentane used was it is "DYTEK" EP (a trademark E.I. du Pont de Nemours and Company). In the tables mean % NCO is the free isocyanate in the terminated glycol; C.R. is that Termination ratio; Eb is the elongation at break; SS is the efficiency of steam fixation; HSE is the heat fixation; LP is the load and UP is the decrease load.

EXAMPLE 1

• A. In a nitrogen-filled glove box were g in a resin kettle 362.85 polytetramethylene ether glycol (Terathane ^® 1800 a trademark of EI du Pont de Nemours and Company, number average molecular weight 1,800) was added and 10 ml of toluene. The mixture was heated to 112 ° C with vigorous stirring for 15 minutes to drive off any water as an azeotrope with the toluene. The glycol was then cooled to 60 ° C and 114.30 g MDI added (2.26 terminating ratio). The glycol / diisocyanate mixture was heated with moderate agitation for 90 minutes to 85 ° C resulting in a terminated glycol prepolymer with 4.5% free isocyanate groups. The prepolymer was cooled to 60 ° C, after which 671 g DMAc with vigorous stirring followed by a diamine chain extender solution (500.98 g, 1.0 N in DMAc, 70 mol% 1,3-diaminopentane and 30 mol% ethylenediamine ) and a solution of an amine chain terminator (17.50 g, 1.0 N diethylamine in DMAc) were added. The intrinsic viscosity of the polymer was 2.01 dl / g. The final concentration of polymer solution was 30% solids in DMAc. There was added 1 wt% "Cyanox" 1790 (a hindered phenolic antioxidant [2,4,6-tris (2,6-dimethyl-4-tert-butyl-3-hydroxybenzyl) isocyanurate] from Cytec Industries, West Patterson, NJ) based on the polymer weight, added to the solution and mixed thoroughly. The solution was dry spun in a conventional manner at 180 m / min to give a 22 dtex monofilament spandex.
• B. Another spandex was used as in Example 1A above made by mixing a chain extender of 60 mole% of 1,3-pentanediamine and 40 mole% of ethylenediamine has been.
• C. A third spandex was prepared as in Example 1A above, but with a terminating Ratio of 1.6 (% NCO 2.2 in the terminated glycol) wherein the only chain extender was ethylene diamine and this material is outside the scope of the invention.

The Properties of these spandex fibers are given in Table I.

TABLE I

table I shows that the spandex of the present invention has a superior Efficiency of steam fixation and heat fixation has and its Elongation, load and decrease load are very good.

EXAMPLE 2

There are polyurethanes from Terathane ^® 1800, 1,1'-methylene-bis (4-isocyanatobenzene), 2.3 terminating ratio, 4.5% NCO in the capped glycol and a mixture of chain extenders of 30 mol.% Ethylene diamine and 70 mol % of the diamines listed in Table II. The procedure used was as described in Example 1. The polymer solution was added in an amount of 1% by weight based on the polymer "Cyanox" 1790. In a conventional manner, monofilament spandex (22 decitex) was dry spun from the DMAc solutions of the polyurethanes at 180 m / min. The steam fixation of the respective spandex was determined and is given in Table II.

TABLE II

Out Table II can be seen that the use of 1,3-diaminopentane of the present invention to a spandex with superior steam fixability leads. Furthermore the spandex made with 1,3-DAP had little fixation (23%) while the spandex made with 1,2-diaminopropane, outside the scope of the invention is an undesirably high Fixation of 43% had.

EXAMPLE 3

There was a polyurethane from Terathane ^® 1800, 1,1'-methylene-bis (4-isocyanatobenzene), 2.0 terminating ratio, 3.6% NCO and a mixture of chain extenders of 90 mol.% 1,3-diaminopentane and 10 mol.% Ethylenediamine produced. No additives were added to the polymer solution. Conventionally, from a DMAc solution of the polyurethane at 730 m / min spandex with 23 decitex was dry spun. The elongation at break was 485%, the steam setting was 39%, the load was 3.5 mN / tex and the decrease load was 1.3 mN / tex.

EXAMPLE 4

There was a polyurethane from Terathane ^® 1800, 1,1'-methylene-bis (4-isocyanatobenzene), 2.0 terminating ratio, 3.6% NCO and a mixture of chain extenders of 80 mol.% 1,3-diaminopentane and 20 mol.% Ethylenediamine produced. No additives were used. In a conventional manner, a spandex with 44 decitex was dry spun from a DMAc solution of the polyurethane at 730 m / min NEN. The elongation at break was 488%, the steam setting was 45%, the load was 6.0 mN / tex and the take-off load was 2.0 mN / tex.

The Examples 3 and 4 illustrate the good fiber properties, with the help of the spandex according to the invention at levels up to 80% to 90 mol.% 1,3-Diaminopentan achievable as a chain extender are. It should be noted that the spinning speeds here much higher were as in the other examples and the steam fixation, the this results, not directly compared with those can be found in the other examples. in view of the high spinning speeds are the results of steam fixation acceptable.

EXAMPLE 5

Into a resin kettle loaded with nitrogen, 75.50 grams of a copolyether glycol based on 87 mole percent tetrahydrofuran and 13 mole percent 3-methyltetrahydrofuran monomers having a number average molecular weight of 3,530 and 10 milliliters of toluene were charged to a resin kettle. The mixture was heated to 112 ° C with vigorous stirring for 15 minutes to drive off any water in the glycol as an azeotrope with toluene. The glycol was then cooled to 60 ° C and 19.48 g MDI added (3.64 terminating ratio). The glycol / diisocyanate mixture was heated to 100 ° C with moderate stirring for 90 minutes, resulting in a terminated glycol prepolymer with 5.0% free isocyanate groups. The prepolymer was cooled to 60 ° C and 147.76 g of DMAc with vigorous stirring followed by a solution of a diamine chain extender (111.02 g, 1.0 N in DMAc, prepared from 70 mole% of 1,3-pentanediamine and 30 mole percent ethylenediamine) and a solution of amine chain terminator (3.50 g, 1.0 N diethylamine in DMAc). No additives are added. The final concentration of polymer solution was 28% solids in DMAc. The polymer intrinsic viscosity was 1.05 dl / g. The polymer solution was cast into films by the solution cast on a polyester film of Mylar ^® trademark of DuPont and the solution was removed using a 0.015 mil doctor blade into strips. The DMAc was removed in a drybox that was purged with dry nitrogen for approximately 16 hours. The tops of the film were dusted with talcum powder and the film / polyester film composites cut into 0.32 cm (0.125 inch) wide and 12.7 cm (5 inch) long strips with a razor with multiple blades. When lifting off the polyester surface talcum powder was applied to the back of the film. The data of stress / strain, steam fixation efficiency, hot wet creep, and heat set efficiency are recorded in Table III as Sample A.

B

gibt den Faserbruch an.

Other polyurethane ureas of similar composition were made and cast into films and the test results shown in Table III. In each case the diisocyanate was MDI and the ethylenediamine was used together with 1,3-diaminopentane. The copolyether glycol contained 87 mol.% Tetrahydrofuran monomer and 13 mol.% 3-methyltetrahydrofuran monomer having a number average molecular weight of 3,530, while it was at the homopolyethers to Terathane ^® 1800's. TABLE III

B

indicates the fiber breakage.

The Examination of the data in Table III shows the improvement in terms of the steam fixation and the load that is possible when the terminating relationship is high. The copolyether glycol also provides higher elongation and increased about that In addition, the steam fixation. Furthermore, these data show that under normal conditions of steam fixation the hot-wet creep of the fibers, with 100% 1,3-DAP (outside the scope of the invention) are undesirably high is what is shown by the fiber break during the test.

EXAMPLE 6

• A. In a nitrogen-filled manipulation chamber 380.00 g of polyester glycol derived from a resin kettle were used the reaction of a mixture of 60:40 ethylene glycol and butanediol with adipic acid, number average molecular weight 3,400, with 10 ml of toluene. The mixture was heated to 112 ° C under vigorous stir for 15 min heated to abatieren any water, and was then until Cooled to 60 ° C, after which 91.02 g MDI (terminating ratio 3.26) were added. The glycol / isocyanate mixture was up 85 ° C below moderate stirring for 120 min heated, resulting in a terminated glycol prepolymer with 4.5% free Isocyanate groups resulted. The prepolymer was up to 60 ° C chilled and 662.39 g DMAc added with vigorous stirring followed by a diamine solution (494.56 g, 1.0 N in DMAc), 70 mol% 1,3-pentanediamine and 30 mol% Ethylenediamine in a solution chain terminator (17.28 g, 1.0 N diethylamine in DMAc). The polymer intrinsic viscosity was 1.00 dl / g. The final concentration of the polymer solution was 30% solids in DMAc. It was 1 wt .-% "Cyanox" 1790 based on added the polymer and thoroughly mixed. The polymer solution was spun into monofilament yarn at 22 dtex at 180 m / min. The obtained test results of this spandex are given in Table N.
• B. Using the procedure described in Example 6A above Procedure was a polyurethaneurea using a polyester having a molecular weight of 2,400, made from 2,2-dimethyl-1,3-propanediol and dodecanedioic acid and lower termination ratios produced and spun dry to spandex. The test results are shown in Table IV.

TABLE IV

As can be taken from Table N, can be a spandex with excellent Properties (high efficiency of steam fixation and heat fixation) obtained with polyester glycols, if these with high proportions of 1,3-diaminopentane and high terminating ratios.

EXAMPLE 7

In a similar manner as in Example 1, three samples of spandex Terathane ^® 1800, and MDI with a termination ratio of 1.6 (2.4% NCO in the capped glycol) and with three different molar ratios of 1,3-diaminopentane to ethylenediamine in the Chain extender mixture prepared as specified in Table V. With these lower amounts of 1,3-diaminopentane, the termination ratios were advantageously maintained near the lower end of the range; the resulting spandex exhibited high steam fixation efficiency, high stress and high unloading load.

TABLE V

Claims (10)

Polyurethane urea polymer based on: Polyester glycol; 1,1'-methylenebis (4-isocyanatobenzene); and one or more diamine chain extender (s) in which one of the Diamine is 1,3-diaminopentane, which is in an amount of at least 5 mol% of the mixture of diamines is present, and wherein the other diamine Ethylenediamine is; where the range of ratios the bis-isocyanate also glycol is 1.5 to 3.7. Polyurethaneurea polymer based on: polyether glycol selected from the group consisting of a homopolymer of tetrahydrofuran and a copolymer of tetrahydrofuran and 3-methyltetrahydrofuran; 1,1'-methylenebis (4-isocyanatobenzene); and one or more diamine chain extender (s) wherein one of the diamines is 1,3-diaminopentane present in an amount of at least 5 mole percent of the mixture of the diamines, and wherein the other diamine is ethylene diamine; wherein the range of ratios of bis-isocyanate to glycol is determined as follows:

The polymer of claim 1, wherein the polyester glycol selected is from the group consisting of a copolyester of ethylene glycol and butylene glycol with adipic acid and a polyester of 2,2-dimethyl-1,3-propanediol and 1,12-dodecanedioic acid; and wherein the chain extender at least about 35 mole% of 1,3-diaminopentane. The polymer of claim 2, wherein 1,3-diamine pentane in an amount of at least about 35 mole%. The polymer of claim 2, wherein the polymeric Glycol a copolyether of tetrahydrofuran and based on the total monomers to 4-20 Mole% 3-methyltetrahydrofuran. The polymer of claim 2, wherein the polymeric Glycol is a homopolyether copolyether of tetrahydrofuran. A polymer according to claim 4, wherein the 1,3-diamine pentane in an amount of at least about 60 mole%. The polymer of claim 3, wherein the 1,3-diamine pentane in an amount of at least about 60 mole%. Spandex spun from polyurethaneurea polymer according to claim 1. Spandex spun from polyurethaneurea polymer according to claim 2.